The present invention relates to a surface for an article having a base structure produced artificially and exerting a self-cleaning effect.
EP-B-0 772 514 discloses self-cleaning structures of articles having an artificial surface structure of elevations and depressions. The distance between the elevations ranges from 5 to 200μ, and the height of the elevations ranges from 50 to 100μ. In addition, at least the elevations are of water-repellent polymers or materials rendered permanently water-repellent. The elevations are not dissolvable by water or water containing detergents.
That solution exhibits a surface having elevations which repel contaminants. A lotus leaf structure is imitated which is known not to be contaminated as a result of self-cleaning, the biological structure of which repels even commercially available adhesives. Despite the remarkable results with respect to self-cleaning effect, the surfaces may be used only to a limited extent, in that either the range of materials to be used in manufacture is greatly restricted or the surface must undergo costly finishing for the purpose of waterproofing. In addition, the process of manufacturing of the disclosed surface is expensive and complicated. Coating processes or shaping processes with high-mesh screens are employed in the manufacture of the disclosed surface which are cost-intensive and difficult to control. Practical experience has shown that “Lotus effect” surfaces produced in this manner often do not yield the desired results as regards self-cleaning.
PCT/WO 93/01047 discloses a surface having a raised thermoplastic film. This surface has a multiplicity of macrocells in the form of elevations extending between these adjacent macrocells. The macrocells have a depth of 0.635μ to 3.81μ. The thermoplastic film has, in addition, at least a plurality of microindentations spaced at intervals ranging from 1.25μ to 6.35μ, that form a randomly distributed sand blast pattern on the film. These microindentations form as an additional structure a second type of elevations having an orientation opposite that of the elevations of the first type, so that the elevations are positioned separately as types on opposite sides of the surface. Such known surfaces, polyolefine foils, for example, such as ones made from polyethylene, with areas of elevations extending between them, are used in particular where special requirements are set for tactile or visual perception, and used for linings for clothing, hygiene or sanitation. Those surfaces possess no antisoiling properties, so that a self-cleaning effect cannot be demonstrated.
EP-A-0 933 388 discloses a structured surface possessing water repellent and/or oil repellent properties, along with low surface energy values. These disclosed surfaces have large water wetting angles. Only with difficulty are they wetted with water to possess a self-cleaning effect. To achieve this effect, a base structure produced by artificial means is provided with two different types of elevations as an additional structure on the surface. Smaller elevations are applied to a superstructure in the form of geometrically larger elevations, which, being immediately adjacent, come in contact with each other. To produce the known elevations and the superstructure as another type of elevations, the latter are simultaneously or in succession mechanically impressed into the surface material, etched in by lithographic processes, or applied by shaping processes or obtained by casting practices. In the case of the mechanical impression process, the effect on the surface is appropriately exerted from the rear side, two types of structural elevations then are formed on its opposite side.
At least some damage to the surface material by the etching agent is to be expected when the structure is etched into this surface material. In the shaping application process, first the elevation structure involved is applied to the surface material by an application roller. This process is expensive and cost-intensive. There is no guarantee that the structure applied will not be separated from the base material again as a function of stress. In addition, the casting, imprinting, etching, and application processes disclosed are not suitable for making large quantities of structured surfaces available in large-scale industrial production. Although this known solution does yield very good results for self-cleaning, its counterpart in nature is in the form of the leaf surface of the nasturtium.
Objects of the present invention are to provide a surface characterized by a very high degree of removal of contaminants and permitting cost-effective large-scale industrial production.
These objects are attained by a surface possessing capillary action in which the quotient of capillary work K and work of adhesion A is greater than 1. The capillaries of the capillary structures exhibit so-called negative capillary rise, that is, liquid is forced from the capillaries. This action is true in particular for liquids where the angle of contact on the structured surface ranges from 90° to 180°. The respective effect of the capillaries on the surface is described by the capillary work K and work of adhesion A. Since the capillary work K draws the drop from the structure, while the work of adhesion A tries to retain the drop in the structure, choice of a value for the quotient of those two kinds of work greater than 1 makes it possible to subject a drop penetrating the capillary opening in wetting action to an opposing force making self-cleaning possible.
In one preferred embodiment of the surface of the present invention, the structure has or forms a capillary where the mean capillary radius rK is smaller than rT, that is, the radius of the smallest drop of water occurring in the environment, a raindrop in particular.
Since drops of different sizes occur in use of the self-cleaning structured surface, it is additionally important in configuration of the structured self-cleaning surface that the capillary radii selected rK be smaller than the radius of the smallest raindrop rT occurring in nature. For this purpose, account is taken of the impact of free falling raindrops which may be dispersed into several small drops on striking any surface.
Consequently, the statement rK<rT must apply to the capillary radius rK of the self-cleaning structure surface for a small drop not to fall into the structure without negative capillary rise to occur in the capillaries. Different capillary radii are then obtained for different fluids such as oil, water, chemical fluids, etc. because of the corresponding properties of the fluids. If the capillaries are produced by geometric structures other than tubules, such as pyramidal, conical, or truncated cone projecting lengths, a mean or average capillary radius rK is to be determined for these structures during their design.
In another preferred embodiment of the surface of the present invention, this surface is formed at least in part of hydrophilic materials, plastic materials in particular, such as thermoplastics and duroplastics especially in the form of polyvinyl chloride, polyterephthalate, polymethyl methacrylate, or polyamide. Unlike the disclosed solutions, a hydrophilic material is employed to increase the degree of antisoiling rather than hydrophobic or oleophobic surfaces. A higher degree of antisoiling surprising to the average expert in this field can be achieved with this hydrophilic material than with the known structures. Since the base structure for the surface is made of a hydrophilic plastic, the material is hygroscopic and absorbs moisture, so that a protective or separating layer possessing improved antisoiling properties is formed on the basis of the water molecule and accordingly the moisture in the material.
In another preferred embodiment of the surface of the present invention, the capillary is made up of a fastening element. The free end of the stalk component is connected to the base structure. On its other end, a fastening element such as a head or hook element is provided. The fastening element and at least a part of the stalk component have at least one capillary opening. In that configuration, fastening elements with interlocking heads and interlocking hooks, also designated as hook and loop fasteners in technical language, may be produced and may be obtained from the applicants' assignee, for example, under the registered trademark “Kletten®”.
The hook and loop fastening material may be detachably connected from the hook side to the corresponding coating material to form a fastener or to the fastening heads of a correspondingly configured fastener element in which the loops of one fastening element detachably engage the heads of the other fastening element. A fastener characterized by a high degree of antisoiling is then obtained. This characteristic is advantageous, especially if such fasteners are used in the area of the clothing industry and automotive technology. If such fasteners are then used, for example, in the area of infant diapers, they repel soiling material, such as even material in the form of baby powder or baby lotion, so that the fasteners designed for the purpose permit reliable fastening of the infant diapers and subsequent disposal while folded.
Preferably, the capillaries as stalk components or as part of the fastening elements are positioned side by side on the surface in such a way that comparable capillaries are again formed by the interstices thereby formed.
The surface, especially if it is configured as an adhesive fastener element, may be produced continuously with its structures by a chill-roll process, also in conjunction with a calendering process. Chill-roll in technical language refers to “sudden cooling or chilling of the extruded plastic material by passage over highly efficient chilling rollers” (see Nentwig, “Kunstoff-Folien” [Plastic Foils], second revised edition, Hansa-Verlag, 2000, page 51). Firstly, this process permits stationary mounting of the capillary structure on the surface, since the latter is an integral part of the base support material in the form of the artificially produced base structure, such as one in the form of plastic foil. Secondly, very large quantities of structured band and foil material can be obtained by the manufacturing technology based on the chill-roll configuration of the process technology, since the texture roller operating in conjunction with a counterhold roller permits virtually continuous operation by means of extrusion into the recesses of the texture roller. A process conducted for this purpose in which dandy rollers are used as texture rollers is described, for example, in DE 198 28 856 C1.
In another embodiment of the surface of the present invention the capillary structure is obtained by a process of depositing drops of a plastic material. A process such as this is described in the subsequently published DE 101 06 705.4. In this process, at least one fastening element is formed in at least one partial area without shaping tools. The plastic material is applied in drops consecutively by at least one application device. The positions selected for deposition of the drops are three-dimensional with respect to the shape of the fastening element to be formed. The structure involved also permits configuration of fastening elements which preferably form the capillary opening in their longitudinal direction.
Other objects, advantages and salient features of the present invention will become apparent from the following detailed description, which, taken in conjunction with the annexed drawings, discloses preferred embodiments of the present invention.
Referring to the drawings which form a part of this disclosure:
The surface shown in
Each capillary 12 has a capillary opening 14 with a capillary radius rK smaller than the radius rT of the smallest drop of water found in nature, a raindrop in particular.
The respective structured surface shown in
The statement K=τhK2·rK2·g·ρ applies to the capillary work.
The following equation applies to the work of adhesion A, especially in the case of cylindrical capillaries:
in which
The capillary-like other structures may, in contrast to the illustration in
Inasmuch as drops of different sizes occur in use of the self-cleaning structured surface, it is also of importance for configuration of this surface that the capillary radii rK be smaller than the radius of the smallest rain drop rT occurring in the environment. The impact of free falling rain drops is also taken into account for this purpose. This drop is on impact with any surface broken into a plurality of small drops, and accordingly also on impact on a self-cleaning structured surface exerting a capillary effect. The following statement applies to the radius rT of the smallest drop which occurs:
in which:
σlg is the surface tension of the liquid,
g is the acceleration of gravity (9.81 ms−2),
ρ is the density of the liquid, and
v is the rate of fall.
It follows that rK<rT must be true of the capillary radius rK of the self-cleaning structured surface for a small drop not to fall into the structure, and thus, for no negative rise to take place in the capillaries. It is only that condition which makes self-cleaning possible. Different capillary radii are obtained for different liquids as a result of the corresponding properties of the liquids.
If the capillaries 12 are used as structures, it is necessary to observe the effect of the capillary forces on a liquid in both directions:
Case A: Liquid is drawn into a capillary (capillary rise hK positive).
Case B: Liquid is forced from the capillary (capillary rise hK negative), capillary depression.
If the drop lies on the structured surface, the drop is situated above the capillaries 12 and the case of interest is case B. The liquid is then forced upward from the capillary 12 into the rising drop against the force of gravity.
There is then obtained a capillary rise hK in a capillary 12.
Capillary rise hK in one capillary 12 thus results:
since σlg·cos θ=σlg−σsl (Young's equation),
in which:
σ is the surface tension values, where
σlg is for liquid-gas,
σsg is for solid-gas and
σsl is for solid-liquid,
θ is the angle of contact of liquid and surface of solid,
ρ is the density of the liquid,
g is 9.81 ms−2 (acceleration of gravity), and
rK is the radius of the capillary 12.
The capillary rise hK in the capillary 12 has a negative value in case B. All quantities in the capillary rise formula are positive. Only the cosine of the angle of contact θ is negative provided that
90°<θ<180°.
In principle the angles of contact must be greater than 90° for the desired effect to occur at all, that is, in order that the liquid be forced from the structures by capillary forces. As a result of roughness of surface, the statement is valid that
cos θ=k cos θ,
in which:
θ is the angle of contact of rough surface,
θ is the angle of contact of smooth surface, and
k is the roughness coefficient (>1).
In addition, the relationship of the radius of the structures to the forces of adhesion is essential in determination of the effect of capillary forces in structured surfaces, since in this situation forces of adhesion act against capillary forces on the wall of the capillary.
In the state of equilibrium, the capillary force acting on the liquid is as great in the opposite direction as the force of gravity of the column of liquid displaced. For purposes of calculation, a fictitious cylinder may be assumed in which the calculated rise of liquid corresponds (in this instance, for example) to ΔhK=10.157 mm in the case of water with θ=110°, ρ=998.2 kgm−3, and rK=0.5 mm).
Capillary work and work of adhesion are calculated rather than the forces for the sake of mathematical comparison.
The capillary work K then equals the product of volume, acceleration of gravity g, density ρ, and the capillary rise hK, with
K=ρhK2·rK2g·ρ
Work of Adhesion in the Straight Circular Cylinder A
Work of adhesion A over the contact surface F:
The foregoing formula applies to a radius rT of the size distribution, in the lowermost area of the drop of water, of raindrops appearing in the environment with a plurality of capillaries used.
The capillary work must be greater than the work of adhesion for the drop not to come in contact with the bottom of the capillary, and for the drop to be evacuated from the recesses and rest on the surface. That condition which results in the advantageous self-cleaning. The quotient K/A is calculated for the purpose of comparison of the capillary work K and the work of adhesion A.
Especially good self-cleaning effects have been obtained when the surface is formed of hydrophilic materials, in particular plastic materials in the form of polyvinyl chloride, polyterephthalate, polymethyl methacrylate, or polyamide. The hydrophilic materials draw moisture into the base structure, and, in this way, form a protective layer against the occurrence of aqueous soiling elements. Use may also be made in the plastic materials of other cross-linked structures, especially ones in the form of acrylate material or materials which are found to be biodegradable.
If the plastic material illustrated in
If the initial material as illustrated in
Another process for producing the surface in the configurations illustrated in
A very advanced self-cleaning effect has been achieved with the structured surface of the present invention. A capillary effect is exerted and the structures used for the purpose may be obtained cost-effectively on an industrial scale and employed for a large number of applications. The base structure 10 with its other structures 12 may be configured as a foil material. The possibility also exists of immediately providing the surface of objects directly with the capillary structure, in particular by application of the drop depositing method described.
In the embodiment illustrated in
In another embodiment comparable to that of
In the embodiment shown in
In the embodiment shown in
The base structure 10 preferably has a thickness of 10μ to 50μ. The capillary depth preferably is greater than 5μ. All tubules or elongated cavities (pores) with very small interior diameters are suitable for use as capillaries (capillary tubes).
Cross-linkable plastics, cross-linkable polyacrylates in particular, are especially well suited as plastic materials for production of the respective capillaries 12, in addition to the base structure 10. If the base structure 10 is configured as a foil or path, the surface may also be employed as that of a shower curtain, tent panel, beach and patio umbrella, and as an article of clothing.
While various embodiments have been chosen to illustrate the invention, it will be understood by those skilled in the art that various changes and modifications can be made therein without departing from the scope of the invention as defined in the appended claims.
Number | Date | Country | Kind |
---|---|---|---|
102 07 194 | Feb 2002 | DE | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
---|---|---|---|---|
PCT/EP03/00308 | 1/15/2003 | WO | 00 | 8/13/2004 |
Publishing Document | Publishing Date | Country | Kind |
---|---|---|---|
WO03/070392 | 8/28/2003 | WO | A |
Number | Name | Date | Kind |
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5180620 | Mende | Jan 1993 | A |
5238623 | Mrozinski | Aug 1993 | A |
5250253 | Battrell | Oct 1993 | A |
5792404 | Cree et al. | Aug 1998 | A |
6162040 | Clune | Dec 2000 | A |
6627133 | Tuma | Sep 2003 | B1 |
6764745 | Karasawa et al. | Jul 2004 | B1 |
6766817 | da Silva | Jul 2004 | B2 |
6946170 | Gerber et al. | Sep 2005 | B2 |
20010037876 | Oost et al. | Nov 2001 | A1 |
20030038408 | Schulte | Feb 2003 | A1 |
Number | Date | Country |
---|---|---|
198 28 856 | Oct 1999 | DE |
101 06 705 | Apr 2002 | DE |
0 772 514 | Dec 1998 | EP |
0 933 388 | Oct 2002 | EP |
WO 9301047 | Jan 1993 | WO |
WO-0050232 | Aug 2000 | WO |
Number | Date | Country | |
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20050153096 A1 | Jul 2005 | US |